Methanol partial oxidation reformer

ABSTRACT

A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

CONTRACTUAL ORIGIN OF THE INVENTION

The United States Government has rights in this invention pursuant toContract No. W-31-109-ENG-38 between the U.S. Department of Energy andThe University of Chicago representing Argonne National Laboratory.

BACKGROUND OF THE INVENTION

This is an improvement in the invention described in U.S. Pat. No.5,248,566 issued Sep. 28, 1993, the disclosure of which is hereinincorporated by reference.

Fuel cells are being developed for use in automotive propulsion systemsas alternatives for the internal combustion engine in buses, vans,passenger cars and other four wheel vehicles. The major motivations fordeveloping fuel cell powered vehicles are low emissions of pollutants,high fuel energy conversion efficiencies, superior acceleration, lownoise and vibration and the possible use of coal or biomass derivedalcohols rather than petroleum-base fuels. Although petroleum basedfuels can also be used. The present invention is directed mostspecifically to systems for using methanol as a fuel.

The two most important operational requirements for a stand-alone fuelcell power system for a vehicle are the ability to start-up quickly andthe ability to supply the necessary power and demand for the dynamicallyfluctuating load. The rapid start-up requirement is obvious.

Alcohols such as methanol are likely fuels for use in fuel cells fortransportation applications. Methanol is a commodity chemical that ismanufactured from coal, natural gas and other feed stocks, while ethanolis often produced from grain. For use in a fuel cell, however, alcoholmust first be converted (reformed) to a hydrogen rich gas mixture. Thedesired features for such a fuel reformer include rapid start-up, gooddynamic response, fuel conversion, small size and weight, simpleconstruction and operation and low cost.

Methanol has been used in steam reforming for providing a hydrogen richgas stream from mobile combustion engines, see Koenig et al. U.S. Pat.No. 4,716,859 and water, as a reaction product from a fuel cell, hasbeen recycled for use in steam reforming of methanol, see Baker U.S.Pat. No. 4,365,006. Steam reforming of methanol is endothermic andcomplicates, by its energy requirements, its use in a vehicle. Supplyingthe hydrogen rich gas on demand in an intermittent variable demandingenvironment is also a difficult requirement to meet and has beenaddressed by Ohsaki et al. U.S. Pat. No. 4,988,580 but this suggestionis not applicable to a small, mobile system. The catalytic exothermicpartial oxidation-reforming of fuels to produce hydrogen-rich gasstreams is known, see Rao U.S. Pat. No. 4,999,993. The use of a partialoxidation reformer had not been used in a vehicle to accomplish thepurposes of this invention prior to the disclosure of the Kumar et al.'566 patent which is satisfactory for its intended purposes, but wasbased on theoretical considerations.

The subject invention is an improvement of that disclosed in the Kumaret al. '566 patent and relates to the use of specific reactor designsand catalyst along with mechanism for controlling the oxygen to methanolmole ratio to control operating temperatures to produce a commerciallyviable system.

SUMMARY OF THE INVENTION

This invention relates to a partial oxidation reformer which has alongitudinal extent at least 1.5 times its diameter and which containsan oxide catalyst for partially oxidizing and reforming mixtures ofwater, air and methanol into a hydrogen containing gas.

The invention, in one aspect, combines a particular oxidation reformerwith a fuel cell for using the hydrogen-containing gas put out by thepartial oxidation reformer and air to produce d.c. power which operatesan electric motor in a transportation vehicle.

Another aspect of the invention is that the partial oxidation reformeris provided with mechanism for introducing methanol and water in smalldroplets and intimately mixing the droplets with air prior to partialoxidation.

The invention consists of certain novel features and a combination ofparts hereinafter fully described, illustrated in the accompanyingdrawings, and particularly pointed out in the appended claims, it beingunderstood that various changes in the details may be made withoutdeparting from the spirit, or sacrificing any of the advantages of thepresent invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of facilitating an understanding of the invention, thereis illustrated in the accompanying drawings a preferred embodimentthereof, from an inspection of which, when considered in connection withthe following description, the invention, its construction andoperation, and many of its advantages should be readily understood andappreciated.

FIG. 1 is a schematic diagram of the partial oxidation reformer of thepresent invention;

FIG. 2 is a graphical representation of the relationship of temperatureand gas concentrations with time during ignition;

FIG. 3 is a graphical relationship of product gas distributions atsteady state as a function of reactant mass velocity;

FIG. 4 is a graphical illustration of the relationships of the transientbehavior of the reformer: hydrogen concentration and temperatures duringa step change in processing rates with the Oxygen/Methanol Mole Ratio of0.25;

FIG. 5 is a graphical representation of the product compositions withhours of operation via partial oxidation reformer;

FIG. 6 is a graphical representation of the relationship between thefeed rates of methanol and air, the current to the igniter and themethanol and the product with the hours of operations; and

FIG. 7 is a schematic illustration of a vehicle incorporating thepartial oxidation reformer and a fuel cell combination.

DESCRIPTION OF THE PREFERRED EMBODIMENT

In a fuel cell system operating on methanol, the overall reaction is:

    CH.sub.3 OH+3/20.sub.2 →CO.sub.2 +2H.sub.2 O        (1)

but the methanol must first be converted to hydrogen by either the steamreforming reaction,

    CH.sub.3 OH(1)+H.sub.2 O(1)→3H.sub.2 +CO.sub.2 ΔH.sub.298 =+131 kJ                                                  (2)

or the partial oxidation reaction,

    CH.sub.3 OH(1)+1/2O.sub.2 →2H.sub.2 +CO.sub.2 ΔH.sub.298 =-155 kJ                                                        (3)

or some combination of the two. For either of these overall reformingreactions, the reaction mechanism involves several steps.

The steam reforming reaction is endothermic, i.e., requires the input ofthermal energy via indirect heat transfer, leading to the need for arelatively large heat exchange surface area and consequently a largereformer. On the other hand, the partial-oxidation reaction isexothermic. No indirect heat transfer is required within the reactor.Further, since the reformer is heated up to its operating temperature bydirect oxidation of the fuel, it starts much more rapidly than a steamreformer. Since no heat transfer is required, the reactor is compact andlightweight. Moreover, the system design is simple and is dynamicallyresponsive to load changes.

The advantages of the partial oxidation reformers are compactness, asimple system design, rapid start-up capability, and good dynamicresponse, are especially attractive for fuel cell systems which have oneor more of the following: space/weight limitations, frequent start-upand shut down, and operation at loads that vary often and rapidly.Transportation fuel cell systems represent an application where all ofthese features are common.

Although reaction (3) shows the partial oxidation reaction taking placewith an oxygen-to-methanol mole ratio of 0.5, which may be preferred atstart-up conditions, this reaction can be conducted at a loweroxygen-to-methanol ratio in which case the product also contains somecarbon monoxide. Reaction (4) shows an example with anoxygen-to-methanol mole ratio of 0.25,

    CH.sub.3 OH(1)+1/4O.sub.2 →2H.sub.2 +1/2CO.sub.2 +1/2COΔH.sub.298 =-13 kJ                            (4)

The carbon monoxide formed is subsequently converted to carbon dioxideand additional hydrogen via the water gas shift reaction. Reaction (5)is the water gas shift reaction:

    CO+H.sub.2 →CO.sub.2 +H.sub.2                       (5)

At an oxygen-to-methanol ratio of 0.25, the reaction is only marginallyexothermic; indeed, the reaction becomes thermally neutral at anoxygen-to-methanol ratio of 0.23. Operating at a low oxygen-to-methanolratio is also advantageous in reducing the amount of nitrogen introducedinto the system.

Referring to FIG. 1, there is a partial oxidation reformer 10 formethanol. It is a compact cylindrical reaction vessel 11 with a totalvolume of 0.8 L. A liquid pump 12 delivers the liquid methanol to anultrasonic nozzle 13 located at the top of the reactor 11. The nozzle 13creates a mist of fine liquid methanol droplets and sprays it into thereactor 11. The air stream is fed in tangentially through inlet 14 fromthe side (similar to a cyclone separator), just above the nozzle 13 tip.

Injecting the liquid methanol as fine droplets permits uniformdistribution of the methanol across the reactor cross-section. It alsoprevents local cold spots that might otherwise be formed by depositionof a large drop of liquid on a surface. The tangentially fed air streamcreates a turbulence which facilitates a mixing between the liquidmethanol droplets and air.

The methanol droplets are carried down by the air stream past anelectrical igniter coil 15. The igniter 15 provides sufficient heat tovaporize part of the methanol to enable the partial-oxidation reactionin the subsequently catalyst section. The igniter mechanism may also bean electrical hot wire, a Pd catalyst, a spark plug or a glow plug.

The catalyst section consists of a ceramic honeycomb 16 (400 channelsper square inch) disks coated with the copper zinc oxide catalyst. Thehoneycombed supports offer the advantages of uniform flow distributionand a low pressure drop within the reactor. The product stream emergesat the bottom of reactor 11. There may be a layer 17 of zirconia pellets(to serve as thermal mass) above the catalyst layer 16.

The air feed rate is used to control the reactor temperatures andhydrogen concentration in the product. The reactor temperatures increasewith increasing oxygen-to-methanol mole ratio. Higher hydrogenconcentration in the reformer can also be achieved by operating at lowoxygen-to-methanol ratios. A ratio of 0.5 or higher is used for rapidstart of the reformer; as the reformer heats up to the operatingtemperatures, the oxygen-to-methanol ratio is reduced to between 0.23-toabout 0.4.

The reactor 11 was operated at various catalyst loadings and at variousmethanol and air feed rates. The reactor performance was monitored byrecording flow rates, temperatures and gas compositions. The product gaswas analyzed for hydrogen, carbon monoxide and carbon dioxide with thehelp of on-line detectors. A gas chromatograph was used to periodicallyanalyze the gas stream for all major components (nitrogen, oxygen,carbon oxides, hydrogen, methane, water and methanol).

The reformer 10 illustrated in FIG. 1 consists of a cylindrical pipe 11with an internal diameter of 5.1 cm (2 in.). Liquid methanol (or amethanol/water mixture) was sprayed into the top of the reactor 11 withan ultrasonic nozzle 13. Air was introduced tangentially at inlet 14 andmixed with the liquid mist as they travelled downward toward thecatalyst 16. A nichcrome igniter 15 is used to start up the reformer 10.

A copper zinc oxide catalyst was supported on honeycomb disks. 5-cm indiameter by 2.5-cm high, weighing ˜30 g each. A number of thermocouplesT_(i) -T₈ were used to record the temperature along the length of thereactor. Part of the reformer product stream was cooled to remove allcondensables and then analyzed for hydrogen, carbon monoxide, and carbondioxide by on-line detectors. Samples of the reformate gas were alsoanalyzed by a gas chromatograph. The reactor has been operated atmethanol liquid flow rates of 25-60 ml/min and air flow rates of 20-54L/min. At 60 ml/min methanol and 54 L/min of air, the gas mass velocitybased on the reactor cross-section is 0.1 gs⁻¹ cm⁻², and the spacevelocity was 1.8 s⁻¹. The steady-state data reported here were obtainedat oxygen-to-methanol ratios of ˜0.25. This lower (than 0.5) ratio wasmaintained to achieve higher hydrogen concentrations in the product and,to prevent the high catalyst temperatures (detrimental to catalyst) thatresult from oxygen-rich feeds.

Ignition Tests

Each test was started with the reactor 10 at room temperature. The airflow was first established at the desired rate. The igniter power wasthen switched on, and the coil 15 was allowed to heat up for 1-10 sbefore the methanol flow was started. A typical plot of temperature andgas compositions versus time is shown in FIG. 2. The temperature justabove the catalyst section (3 cm below the igniter coil) is given bycurve T₁. The concentrations of hydrogen and carbon oxides (CO_(x)=CO----CO₂), on a dry basis, are also shown in FIG. 2. The T₁ curveshows that the ignition takes place within 5 seconds after the methanolflow is started. The first traces of carbon oxides appear 7 secondslater, and the first trace of hydrogen is observed 23 seconds after themethanol flow is started. The delay between the CO_(x) and H₂ curves ispartly due to the hydrogen analyzer having a slower response time thanthe infrared analyzers for the carbon oxides.

Steady State Tests

The reactor was operated at steady-state conditions at various methanoland air flow rates. The concentrations of hydrogen, carbon monoxide, andcarbon dioxide as a function of the reactant gas mass velocity are shownin FIG. 3. For each of these tests the oxygen-to-methanol molar ratiowas maintained at ˜0.25. The data indicate that the gas compositions areslightly affected by the mass velocity: H₂ and CO₂ decrease, and COincreases at higher mass velocities. Over the range of mass velocitiestested, hydrogen various from 37% to 39%; carbon monoxide 16% to 18% andcarbon dioxide 8% to 9%. The product stream was found to contain 1-4%methanol and an average of 1.5% methane. The product stream, when passedthrough a water-gas shift reactor, would convert all the unreactedmethanol and the carbon monoxide to carbon dioxide and hydrogen. Thus,the shifted reformate (neglecting further conversion of the 1-5%unreacted methanol in the gas) would yield a product containing ˜47%hydrogen (dry basis). This value is 9% lower than the theoreticalmaximum for these reaction conditions.

Transient Tests

An important requirement of reformers for transportation fuel cellsystems is their ability to provide varying amounts of hydrogen ondemand, while maintaining the product gas compositions. The dynamicresponse of the reactor 10 was tested by imposing a step change in thereactant flow rates while maintaining a constant oxygen to methanolratio. An example is shown in FIG. 4, where the methanol flow rate wasincreased by 33%, from 30 to 40 ml/min, accompanied by a proportionalincrease in the air flow rate. The resulting effect on hydrogenconcentration and the temperatures just above and just below thecatalyst bed, T₄ and T₈, respectively, are shown in the figure. If thehydrogen production rate had not increased after the step change, theincrease in the air flow alone would have dropped the hydrogenconcentration to 28%. The hydrogen curve in the figure, however, showsonly a minor (1.5%) and temporary drop to 30%. This indicates that theamount of hydrogen produced also increased with the increase in feedrate. The hydrogen concentration returns to its original level in ˜80seconds. Among the temperature curves, T₈ shows a damped response,compared to T₄ because of the thermal mass (catalyst and walls) betweenthe two thermocouples.

Referring to FIGS. 5 and 6, there is shown the relationships for themethanol and air feed rate as well as the amperage to the ignition coilfor almost fifty hours of operation and the product mix (FIG. 5) as wellas the unreacted methanol in the product (FIG. 6). Of importance is thefact that the amount of hydrogen in the product stays relativelyconstant between about 45 and 50% even during variations in the methanolfeed rate and the amount of methanol in the product also remainsrelatively constant if under 10% showing that over 90% of the methanolis reacted in the reformer of the present invention.

Referring now to FIG. 7, there is illustrated an automobile 40representative of the type of vehicles in which the subject invention isuseful. The vehicle 40 is provided with a pair of front wheels 41, apair of rear wheels 42, and an electric motor 50 connected to one of thepairs 41, 42 as by a drive shaft 51 and is electrically connected bysuitable means 52 to a battery 55. The battery 55 can be used to startthe vehicle 40 in the same manner batteries function with internalcombustion engines and to run accessories. A partial oxidation reformer10 of the type previously described, is in liquid or gas communicationwith a fuel tank 60 and is connected to a fuel cell 20 of the typepreviously described. An afterburner 30 is connected to the off gasesfrom the negative electrode or anode 21 of the fuel cell and is used toreact the remaining hydrogen in the gas leaving the anode 21 to extractheat therefrom for either heating or cooling the passenger compartmentof the automobile 40, as required. A motor controller 70 is interposedbetween the fuel cell 20 and the electric motor 50 and coordinates thedc power output from the fuel cell 20 and the variable speedrequirements for the motor 50. Such motor controllers are well known inthe art. Also in FIG. 7, there is illustrated a single feed from thefuel tank 60 to the partial oxidation reformer 10, it may be thatmultiple feeds will be provided to the partial oxidation reformer 10.Moreover, it is possible that the partial oxidation reformer 10 will bea multiple zone reformer, with the final zone thereof containing eitheran oxidation catalyst for converting carbon monoxide to carbon dioxideor containing a methanation catalyst for converting carbon monoxide tomethane.

The main object of this invention is obtained by the combination of thepartial oxidation reformer 10 and the fuel cell 20 which provides rapidresponse to variable acceleration demands by the motor 50 due to theexothermic reaction, thereby obviating the need for thermal energy inputto the partial oxidation reformer 10 during periods of acceleration orincreased power demand.

Other objects of this invention have been attained by the novel partialoxidation reformer 10 disclosed having means for mixing droplets ofmethanol and air in a turbulent zone in the reactor, alone or incombination with a fuel cell suitable for a vehicle and in combinationwith the necessary components for a vehicle.

A variety of catalysts may be used, preferably the catalyst is an oxidecatalyst and more preferably, the catalyst is one or more of copperoxide-zinc oxide, FeZnO and cobalt supported on silica. The copperoxide-zinc oxide is preferred and, as previously indicated, it ispreferred to be supported on a honeycomb support for the purposes andadvantages hereinbefore set forth.

At initial start-up, it is preferred that the oxygen to methanol moleratio be higher than 0.5; however, a steady state is preferred that theoxygen to methanol mole ratio be in the range of from about 0.23 toabout 0.4. By controlling the oxygen to methanol mole ratio, thetemperature of the reactants in contact with the catalyst is controlled.Preferably, the temperature of the reactants in contact with thecatalyst is less than about 500° C., and more particularly less thanabout 450° C. The preferred temperature is between about 350-400° C.

Another important aspect of the present invention is the sizedistribution of the methanol droplets, it being preferred that the sizedistribution be in the range of from about 20 to about 50 micrometers.It is also advantageous to have the droplet size be less than about 50micrometers and less than about 100 micrometers will provide advantages.

Another important aspect of the invention is the turbulence generated byintroducing the air through the inlet 14 tangentially to the finedroplets of methanol introduced through the ultrasonic nozzle 13. Byintroducing the air tangentially, turbulence is encouraged andtherefore, intimate mixing of the air and methanol occurs and also helpsprevent liquid droplet deposition on the reactor wall.

It is contemplated that a minor amount of water will be added with themethanol in order to facilitate conversion of the carbon monoxide viathe water shift reaction previously set forth to carbon dioxide. Theamount of water in the methanol is preferably less than about 50 volumepercent and more preferably in 20-30% volume range.

Because it is disadvantageous for large droplets of liquid to contactthe catalyst bed 16, there may be inserted between the catalyst bed 16and igniter coil 15, a bed of ceramic particles, for instance, zirconia.These particles may be 1/4 inch pellets of zirconia whose purpose issimply to insure that liquid drops of water and methanol do notintermittently contact the active catalyst. If the catalyst is contactedwith too much liquid, the temperature of the catalyst drops and thecatalyst may become temporarily inert, until it heats up again.

The present invention is particularly useful with fuel cells of the typedescribed in FIG. 2 of the incorporated '566 patent, with the productfrom reactor 10 being directed to the anode of the fuel cell illustratedin the '566 patent.

The methanol partial oxidation reformer's advantages can best bedescribed relative to the other reformers being developed or used withfuel cell systems. These prior art reformers are based on the steamreforming reaction, where the reactants, methanol and water, are firstvaporized and preheated before they can be fed into the reactor. Theinventive partial oxidation reformer requires no pre-vaporization orpreheating.

The steam reforming reaction itself is strongly endothermic and soconsiderable heat must be provided in order to maintain the reactortemperatures. Since the heat transfer is indirect, i.e., transferredfrom across a solid wall, the required rate of heat transfer isaccomplished with a large heat transfer area. Consequently, the reactordesigns become complex, large and heavy. Moreover, a burner is requiredto generate the heat that is to be provided to the reactor. The partialoxidation reformer, in contrast, is a simple cylindrical piece ofhardware 10. No heat exchange surfaces are required, and therefore, thistype of reactor is compact and lightweight.

During cold starts, the steam reformer catalysts must be heated bypassing hot gases on the other side of a wall. This is a slow processand requires a long time. For example, the start-up times for the steamreformer in the DOE fuel cell takes -45 minutes to reach operatingtemperatures. The partial oxidation reformer operates on an exothermicreaction which heats up the gas stream and the catalyst simultaneously.This enables this reactor 10 to have very short start-up times. Themethanol partial oxidation reformer developed herein has reachedoperating temperatures within 1 minute (FIG. 2).

Fuel cell systems using steam reformers are limited in their dynamicresponse. This is because during load changes both feed and heat inputrates into the reformer need to change simultaneously. While the feedrate can be increased rapidly, the heat input is much slower because itoccurs by indirect heat transfer. The partial oxidation reformerrequires no indirect heat exchange and therefore can respond to loadchanges as fast as the feed rates can be changed.

While there has been disclosed what is considered to be the preferredembodiment of the present invention, it is understood that variouschanges in the details may be made without departing from the spirit, orsacrificing any of the advantages of the present invention.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
 1. A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, a water and an air inlet and an outlet, igniter mechanism in said chamber for igniting a mixture of methanol and air, a partial oxidation catalyst in said chamber spaced from said inlet for converting methanol and oxygen to carbon dioxide and hydrogen, and means for controlling the oxygen to methanol mole ratio to provide continuous exothermic partial oxidation reactions of methanol and air producing hydrogen gas, controlling and maintaining the oxygen to methanol mole ratio in the range from between about 0.25 to about 0.4 for continuous operation and at higher values for start-up operation.
 2. The partial oxidation reformer of claim 1, wherein said chamber is cylindrical having a ratio of the length to the diameter of not less than about 1.5.
 3. The partial oxidation reformer of claim 2, and further comprising means for forming the methanol at the inlet into droplets having a diameter of less than 100 micrometers.
 4. The partial oxidation reformer of claim 3, wherein the methanol droplets have a size less than about 50 micrometers.
 5. The partial oxidation reformer of claim 3, wherein the methanol droplets have a size distribution in the range of from about 20 to about 50 micrometers.
 6. The partial oxidation reformer of claim 3, wherein said methanol droplets are introduced into said reactor parallel to the longitudinal axis of said chamber and said air inlet introduces air to said chamber tangentially to the longitudinal axis of said chamber.
 7. The partial oxidation reformer of claim 1, wherein said means to control the oxygen to methanol mole ratio is operated to maintain a temperature of the reactants in contact with said catalyst in the reformer at less than about 500° C.
 8. The partial oxidation reformer of claim 1, wherein said means for controlling the oxygen to methanol mole ratio is operated to maintain a temperature of the reactants in contact with said catalyst in the reformer of less than about 450° C.
 9. The partial oxidation reformer of claim 1, wherein said means for controlling the oxygen to methanol mole ratio is operated to maintain a temperature of the reactants in contact with said catalyst in the reformer of less than about 400° C.
 10. The partial oxidation reformer of claim 1, and further comprising means for forming the methanol into droplets and wherein air is mixed with the methanol droplets to form a mist at an end of the reactor away from said outlet.
 11. The partial oxidation reformer of claim 10, wherein the catalyst is CuO--ZnO.
 12. The partial oxidation reformer of claim 1, wherein the catalyst is an oxide.
 13. The partial oxidation reformer of claim 12, wherein the weight of catalyst is not less than 11 kg per liter per minute of liquid methanol.
 14. The partial oxidation reformer of claim 1, wherein said igniter mechanism is one or more of an electrical hot wire, a Pd catalyst, a spark plug or glow plug.
 15. The partial oxidation reformer of claim 1, wherein said igniter is electrically operated.
 16. The partial oxidation reformer of claim 1, wherein a bed of ceramic pellets is positioned between said inlets and said partial oxidation catalyst.
 17. A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, a water and an air inlet and an outlet, igniter mechanism in said chamber for igniting a mixture of methanol and air, a partial oxidation catalyst in said chamber spaced from said inlet for converting methanol and oxygen to carbon dioxide and hydrogen, and means for controlling the oxygen to methanol mole ratio to provide continuous exothermic partial oxidation reactions of methanol and air producing hydrogen gas, forming the methanol into droplets and mixing air with the methanol droplets to form a mist at an end of the reactor away from said outlet.
 18. A partial oxidation reformer comprising a longitudinally extending chamber having inlets for liquid methanol, water and air and an outlet, mechanism for forming the methanol and water in droplets having diameters less than 100 micrometers, igniter mechanism for igniting a mixture of methanol and air, a partial oxidation catalyst selected from the group consisting of CuO--ZnO, FeZnO and Co supported on SiO₂ in said chamber spaced from said inlets for converting methanol and oxygen to carbon dioxide and hydrogen, and means for controlling the oxygen to methanol mole ratio to provide continuous exothermic partial oxidation reactions of methanol and air producing hydrogen gas.
 19. The partial oxidation reformer of claim 18, wherein said igniter mechanism is one or more of an electrical hot wire, a Pd catalyst, a spark plug or glow plug and said methanol droplets have a diameter less than about 50 micrometers.
 20. The partial oxidation reformer of claim 19, wherein said means for controlling the oxygen to methanol mole ratio is operated to maintain the ratio between about 0.25 to about 0.4 for continuous operation and at higher values for start-up operation.
 21. The partial oxidation reformer of claim 20, wherein said methanol droplets are introduced into said reactor parallel to the longitudinal axis of said chamber and said air inlet introduces air to said chamber tangentially to the longitudinal axis of said chamber. 